Angewandte Chemie International Edition in English

Cover image for Vol. 18 Issue 11

November 1979

Volume 18, Issue 11

Pages 809–885

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Bonding Properties of Cyclopropane and Their Chemical Consequences (pages 809–826)

      Prof. Dr. Armin de Meijere

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908093

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      As a small ring with “double bond” character the first member of the cycloalkane series occupies a special position. In recent years increasing use has been made of the special properties of cyclopropanes in developing new synthons (E[DOUBLE BOND]CO2C(CH3)3).

    2. Conformational Analysis by Photoelectron Spectroscopy (pages 826–837)

      Prof. Dr. Martin Klessinger and Prof. Dr. Paul Rademacher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908261

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      The study of a molecule is usually incomplete if no account is taken of its conformation. Conformational analysis by PE spectroscopy complements conventional methods in case where orbital interactions depend upon the dihedral angle. Hydrazines and biphenyls are prominent examples.

    3. Catalytic Reactions with Hydrosilane and Carbon Monoxide [New synthetic methods (30)] (pages 837–846)

      Prof. Dr. Shinji Murai and Prof. Dr. Noboru Sonoda

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908371

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      “Oxo synthesis with hydrosilane instead of H2 would be one fitting description of the novel reactions with the reagent R3SiH/CO. It functionalizes olefins, cleaves cyclic ethers, inserts into aldehydes RCHO [to give (1)] and permits further promising reactions. CO2(CO)8 is the preferred catalyst.

    4. Neurophysins: Molecular and Cellular Aspects (pages 846–860)

      Prof. Dr. Roger Acher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908461

      Transport of the peptide hormones oxytocin and vasopressin from the hypothalamus to the hypophysial posterior lobe involves the neurophysins, which are proteins made up of ca. 95 amino acid residues. Biosynthesis and transformation of secretory proteins (pro- and prepro-proteins) are gradually being unraveled by present-day research.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis and X-Ray Structure Analysis of a Mo Complex with η2-Coordinated Benzaldehyde; Transformation of a CO Ligand by Double α-Addition (pages 861–862)

      Prof. Dr. Henri Brunner, Dr. Joachim Wachter, Prof. Dr. Ivan Bernal and Michael Creswick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908611

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      Molybdenum serves as spiro-atom in the complex (3) formed from (1), R [DOUBLE BOND] CH3, and PhMgBr in the molar ratio of 1:2. One of the two CO groups is transformed into C,O-coordinated benzaldehyde. Ring contraction (1) [RIGHTWARDS ARROW] (2) is already known.

    2. Thermodynamically Controlled Stereoselective Synthesis of Geissoschizine (pages 862–863)

      Dipl.-Chem. Werner Benson and Prof. Dr. Ekkehard Winterfeldt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908621

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      Stereoconvergence is the aim of economic syntheses of natural products. Tedious saparation of the geissoschizine intermediate (3) from the by-product (1), which arises because of steric interactions between R and CH3, is avoided by hydrolyzing and cyclizing the mixture to the single dilactam (2) with trifluoroacetic anhydride. Regioselective ring opening leads only to (3).

    3. Enantioselective Synthesis of α-Methyl-α-aminocarboxylic Acids by Alkylation of the Lactim Ether of cyclo-(L-Ala-L-Ala) (pages 863–864)

      Prof. Dr. Ulrich Schöllkopf, Dr. Wolfgang Hartwig and Ulrich Groth

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908631

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      Preparatively valuable asymmetric amino acid syntheses must be simple to carry out, give yields of >90%, and, where appropriate, permit recovery of the chiral auxiliary agent. These demands are met by the new synthesis via cyclo-(L-Ala-L-Ala).

    4. Enantioselective Oxidation by a Chiral Acylaminyl Oxide (pages 864–865)

      Dr. Corrado Berti and Prof. Dr. M. John Perkins

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908641

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      A new oxidizing agent having remarkable properties has been found in the readily accessible chiral radical (1). It preferentially oxidizes one enantiomer of the test substances D, L-benzil and D, L-benzion, so thet the other enentiomer accumulates. The reactivity and enantioselectivity of (1) should be enhanced by other substituents.

    5. Thiocarbonyl-Metal Complexes from CSSe (pages 865–866)

      Prof. Dr. Helmut Werner and Dipl.-Chem. Oswald Kolb

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908651

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      Use of CSSe as a source of CS should facilitate the synthesis of thiocarbonylmetal complexes or actually make it possible in some cases. The first examples are (1) and the compound C5H5(PMe3)Rh(CS) obtained from the corresponding ethylene complex.

    6. Cyclic Systems by Palladium-Catalyzed Oxidation of Diolefins (pages 866–867)

      Dr. Andreas Heumann, Dipl.-Chem. Marius Reglier and Prof. Dr. Bernard Waegell

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908661

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      Substituted bi- and polycyclic compounds are accessible from diolefins such as (1), (3), and (5) by reaction with PdCL2 as catalyst in the presence of CuCL2/HOAc/NaOAc. The yields of reactions (3) [RIGHTWARDS ARROW] (4) (77%) and (5) [RIGHTWARDS ARROW] (4) (40%) suggest that (3) has the “correct” stereochemistry for ring closure.

    7. Mechanistic Aspects of the Palladiun-Catalyzed Cyclization of 5-Methylenecyclooctene (pages 867–868)

      Dr. Andreas Heumann, Dipl.-Chem. Marius Reglier and Prof. Dr. Bernard Waegell

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908671

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      An insight into the course of the Pd-catalyzed oxidation of diolefins is provided by reaction of 5-methylenecyclooctene (1) with PdCl2/CuCl2/HOAc/NaOAc to give the bicyclic compounds (2) to (5). In benzene, the diolefin (1) reacts with Pd(PhCN)2Cl2 to form the isolable σ-π complex (6) which cyclizes in hitherto unexplained manner to compounds (2) to (5).

    8. Unusally High Asymmetric Induction in the Photochemical Formation of Oxetanes (page 868)

      Prof. Dr. Hans Gotthardt and Dipl.-Chem. Wolfgang Lenz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908681

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      Asymmetric reactions giving products of high enantiomeric purity are of topical interest in synthetic chemistry. An example is the addition of ([BOND])-menthyl phenylglyoxylate (1) to dimethylbutene. The product consists of 76.3% of one diastereomer and 23.7% of the other. i.e. its enantiomeric purity is 53% (R[DOUBLE BOND]([BOND])-C10H19).

    9. Multiple Cyclopropylmethyl-Cyclobutyl Rearrangements in a Pentaspirohexadecanol (pages 868–869)

      Priv.-Doz. Dr. Lutz Fitjer and Detlef Wehle

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908682

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      Production of coronanes of type (1) by a cascade of rearrangements does not appear impossible: a cascade of cyclopropylmethyl-cyclobutyl rearrangements could be initiated in the case of (3). Depending upon the conditions, it gives (4) or (5) and proceeds via four intermediates (GC analysis).

    10. Formation of Phenyl Cations in the Sovolysis of a Dienynyl Trifluoromethanesulfonate (pages 870–871)

      Prof. Dr. Michael Hanack and Dipl.-Chem. Ulrich Michel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908701

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      The first solvolytically generated phenyl cation owes its formation to a trick: cyclization and solvolysis of (1) are performed in one step. No phenyl compounds of any kind could be solvolyzed to phenyl cations.

    11. Spontaneous Rearrangement of a Carbene- to a Carbyne Complex: C,Cr Migration of a Sn(C6H5)3 Group (page 871)

      Prof. Dr. Ernst Otto Fischer, Dr. Helmut Fischer, Dr. Ulrich Schubert and Dr. Richard B. A. Pardy

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908711

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      Fresh light is thrown upon the rearrangements of carbene complexes into carbyne complexes by the spontaneous reaction (1) [RIGHTWARDS ARROW] (2). It is quantitative at room temperature, does not involve an ionic mechanism and refutes the idea that the migrating heteroatom X in (CO)5CrC(NEt2)X must have a lone pair.

    12. Influence of 1,2-Functionalization with [BOND]C[TRIPLE BOND]N, [BOND]CH[DOUBLE BOND]NR, or [BOND]CH[DOUBLE BOND]O on the Stability of the Cyclobutane System (page 872)

      Prof. Dr. Karl-Dietrich Gundermann and Dipl.-Chem. Paul-Josef Hnida

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908721

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      Studies on the extent of possible substitution of cyclobutane led to surprising results. (1), R [DOUBLE BOND] alkyl, aryl, is known to arise by spontaneous dimerization of acrylonitriles whereas the analogous aldehyde (3) can only be detected by formation of the “Diels-Alder dimer” (4), R[DOUBLE BOND]CH3 (via methylthioacrolein). (2) was not isolated; its product with iPrNH2 decomposes only at 130°C.

    13. The First 2,3,5,6-Tetraphosphabicyclo[2.2.0]hexane (pages 872–873)

      Prof. Dr. Rolf Appel, Dipl.-Chem. Volker Barth, Dr. Mechthild Halstenberg, Prof. Dr. Gottfried Huttner and Dipl.-Chem. Joachim von Seyerl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908722

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      Tetraphosphabicyclohexanes were hitherto unknown. The first example to be characterized by X-ray methods is (1), the product of reaction between phosgene and PhP(SiMe3)2. Stereoscopic drawings clearly show the pronounced twisting in the molecule.

    14. The First 1,3,4,6-Tetraphospha-1,5-hexadiene, a Molecule with Fluxinonal Bonds (Identical Tetraphospha Cope Rearrangement) and Configurational Isomerism (pages 873–874)

      Prof. Dr. Rolf Appel, Dipl.-Chem. Volker Barth, Dr. Fritz Knoll and Dr. Ingo Ruppert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908731

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      PhP[DOUBLE BOND]CR[BOND]PPh[BOND]PPh[BOND]CR[DOUBLE BOND]PPh, R[DOUBLE BOND]NPh[BOND]SiMe3, exhibits degenerate Cope rearrangement and configurational isomerism. The clear analogy between the reactions of this methylenephosphane and corresponding alkenes shows that the P[DOUBLE BOND]C bond of this compound hardly has the ylidic character of methylenephosphoranes.

    15. Tetracarbanilanilidodichromium(II): A Clue to the Understanding of the CrCr Quadruple Bond (pages 874–875)

      Prof. Dr. F. Albert Cotton, Dr. William H. Ilsley and Dr. Wolfgang Kaim

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908741

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      “Normal” and “supershort” CrCr quadruple bonds have been found in complexes. What decides whether the interatomic distance is ca. 2.2–2.5 or < 1.9 Å? The new complex (1) confirms the proposition that axial legands–coordinated solvent molecules in this case–considerably lengthen the bond.

    16. Metalated 2-Alkynyl- and 1,2-Alkadienyl 2-Tetrahydropyranyl Ethers: Versatile Building Blocks for Furan Syntheses (pages 875–876)

      Chem. techn. Manfred Stähle and Prof. Dr. Manfred Schlosser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908751

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      A one-pot furan synthesis utilizes the double lithiation of alkynyl tetrahydropyranyl ethers. These reactions are facilitated by the acetal group.

    17. Structure of the Primary Adduct of a Phosphorus Ylide and Fluorenone (pages 876–877)

      Prof. Dr. Hans Jürgen Bestmann, Dipl.-Chem. Kurt Roth, Dr. Eberhard Wilhelm, Dr. Reinhild Böhme and Prof. Dr. Hans Burzlaff

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908761

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      The postulated ligand shift process (3) [RIGHTWARDS ARROW] (4) in the Wittig reaction is proved indirectly by the structure and behavior of the primary adduct from a cyclic phosphorus ylide and fluorenone. This primary adduct is too rigid to rearrange to (4).

    18. Phosphadiarsiranes (pages 877–878)

      Prof. Dr. Marianne Baudler and Dipl.-Chem. Dietrich Habermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908771

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      The first three-membered rings to contain 4th row elements are the phosphadiarsiranes (1) and (2) which prepared as shown below. (2) is stable at room temperature. Both compounds are formed as diastereomers; the isomer having trans tert-butyl groups is the more stable.

    19. N-Nitroso Sugar Amino Acids (pages 878–880)

      Prof. Dr. Kurt Heyns, Dipl.-Chem. Siyka Röper, Dr. Harald Röper and Dipl.-Chem. Bernd Meyer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908781

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      Nitrosamines in foods are notorious as carcinogens. Sugar amino acids can also form N-nitroso derivatives with nitrite, possibly during the processing of certain foods or in the stomach. The first compounds of this kind have now been synthesized.

    20. Diarylsulfur(VI) Oxide Difluoride by Direct Fluorination of Sulfoxides (pages 880–881)

      Dr. Ingo Ruppert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908801

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      Use of fluorine as fluorinating agent permits the first transformation of sulfoxides (1) into the title compounds (2) under mild conditions in the liquid phase. The formation of an oxo cation from (2) with a new fluoroorgano periphery (R [DOUBLE BOND] aryl) is remarkable.

    21. Polar [4+2]- and [4+4]-Photocycloadditions: Effects of Hybridization in Diradicals (pages 881–882)

      Univ.-Doz. Dr. Gerd Kaupp and Heinz-Willi Grüter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908811

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      The control of photochemical reactions by polar substituents is of value for preparative applications. For example, anthracene (1a) reacts with butadiene to give the [4+2]- (2a) and the [4+4] adduct (3a) in the ratio of 20:1. The carbonitrile (1b), on the other hand, leads to (2b), (3b), and (4) (secondary product of a (3b)-isomer) in the ratio of 1:3.2:13.3. The polar substituent thus suppresses the [4 + 2] reaction (a: X [DOUBLE BOND] H; b: X [DOUBLE BOND] CN).

    22. Quantitative Trace Analysis of Thallium in Biological Material (pages 882–883)

      Dr. Christoph Achenbach, Dr. Rolf Ziskoven, Dr. Ferdinand Koehler, Dipl.-Chem. Ute Bahr and Dr. Hans-Rolf Schulten

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908821

      The pharmacokinetics of the poisonous element thallium have been examined directly by field desorption mass spectrometry from very small tissue samples. After oral administration of 160 mg/kg to mice, concentrations of 10−4 mol/1 were found in organs. While the teratogenic dose 50% is lower than the lethal dose 50% by a factor of 40, some 12.5% of fetal malformations still occur at 1/1000 of the lethal dose.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews

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